US3219703A - Manufacture of diarylamines from nitroaromatics - Google Patents

Manufacture of diarylamines from nitroaromatics Download PDF

Info

Publication number
US3219703A
US3219703A US86606A US8660661A US3219703A US 3219703 A US3219703 A US 3219703A US 86606 A US86606 A US 86606A US 8660661 A US8660661 A US 8660661A US 3219703 A US3219703 A US 3219703A
Authority
US
United States
Prior art keywords
carbon
radical
ketone
hydrocarbon
heating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US86606A
Inventor
Harry W Kilbourne
James E Van Verth
Gene R Wilder
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Monsanto Co
Original Assignee
Monsanto Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Monsanto Co filed Critical Monsanto Co
Priority to US86603A priority Critical patent/US3219705A/en
Priority to US86606A priority patent/US3219703A/en
Priority to DEM51653A priority patent/DE1280253B/en
Priority to GB4035/62A priority patent/GB975097A/en
Application granted granted Critical
Publication of US3219703A publication Critical patent/US3219703A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S524/925—Natural rubber compositions having nonreactive materials, i.e. NRM, other than: carbon, silicon dioxide, glass titanium dioxide, water, hydrocarbon or halohydrocarbon
    • Y10S524/929—Natural rubber broadly disclosed, nonclaimed

Definitions

  • One embodiment of the invention relates to manufacture of diphenylramines from nitroaromatics and alicyclic ketone, which ketone serves as a source of a second aryl group.
  • the process involves heating nitroaromatic and a molar excess of cyclohexanone or other six-membered alicyclic ketone with dehydrogenation catalyst.
  • the course of the reaction is obscure and evidently involves a complicated series of reactions. These are carried out simultaneously without isolating intermediate.
  • the invention is not limited to any theory or opinion as to the mechanism by which the desired products form.
  • Aromatization requires alicyclic ketones containing six carbon atoms in the ring to which the keto group is attached but substituents may be present in this ring and condensed rings are suitable.
  • Examples comprise cyclohexanone, 2 methylcyclohexanone, 3 methylcyclohexanone, 4 methylcyclohexanone, 3,4 dimethylcyclohexanone, 2,S-dimethylcyclohexanone, 4-ethylcyclohexanone, 4-propylcyclohexanone, 4-isopropylcyclohexanone, 4- butylcyclohexanone, 4-tert.butylcyclohexanone, 2-ethylcyclohexanone, alpha-tetralone, beta-tetralone and 2- propylcyclohexanone.
  • unsaturated ketones are also useful, as for example, carvenone, menthone and 3,S-dimethyLZ-cyclohexen-l-one.
  • Ketones containing a quaternary carbon in the ring react poorly in the present process.
  • the process is especially applicable to nitroaromatic hydrocarbons but is not confined thereto.
  • the aromatic nucleus containing one or more nitro groups may contain hydrocarbon substituents but readily reducible substituents are undesirable. Hydrocarbonoxy groups or fluoro substituents may be present.
  • a variety of diarylamines can be made by the process of this invention.
  • Suitable nitrocompounds comprise o-ethoxynitrobenzene, p-dinitrobenzene, m-dinitrobenzene, l-nitronaphthalene, 2-, 3- and 4-nitrotoluene, 4-nitroanisole, 2,4-dinitrotoluene, 4-nitrodiphenyl, p-propoxynitrobenzene, p-ethoxynitrobenzene, p-iso propoxynitrobenzene, p-ethylnitrobenzene, p-propylnitrobenzene, p-isopropylnitrobenzene, m-ethylnitrobenzene, p-amylnitrobenzene, p-hexylnitrobenzene, p-octylnitrobenzene, p-decylnitrobenzene, p-dodecylnitrobenzene, mbutylnitrobenzene, m-tert.-butylnitrobenzene,
  • N-alkylnitroanilines suitable as reactants comprise those in which the alkyl group is methyl, ethyl, propyl, isopropyl, butyl, tert.-butyl, see-butyl, isobutyl, amyl, pentyl, hexyl, octyl, tert.-octyl, see-octyl, nonyl, decyl, undecyl, dodecyl, hexadecyl and the like.
  • the alkyl group increases in size amount of by-products is reduced.
  • dehydrogenation catalysts are known and a variety are commercially available. In general, hydrogenation catalysts also function as dehydrogenation catalysts. Examples of dehydrogenation catalysts are rhodium, ru-- thenium, platinum, palladium, Raney nickel, Raney cobalt, copper chromite, iridium, osmium, oxides of chromium and oxides of molybdenum. For the purposes of the present invention palladium is much to be preferred, is effective under milder conditions and results in higher yields. It will be appreciated, however, that other dehydrogenation catalysts are contemplated and the desired products have been prepared from reactions with other catalyst systems.
  • the catalyst is supported on charcoal, asbestos, alumina, pumice, kieselguhr, silica gel or barium sulfate. Amounts as low as 1% of 5% palladium on carbon give satisfactory results.
  • the amount of catalyst expressed as percent by weight of the final product expected from the reaction assuming theoretical yield, will depend upon the reaction rate required. Amounts within the range of 1%12% catalyst (5% palladium on carbon) efficiently catalyze the reactions although these are not the absolute limits.
  • the reactions may be effected in the presence of elemental hydrogen providing the hydrogen concentration is not so high as to make hydrogenation predominate over dehydrogenation. The presence of hydrogen gas sometimes mitigates catalyst poisoning.
  • the optimum temperature for heating usually will, fall with the range of ISO-250 C. depending upon the particular ketone reacted. These are not the absolute operating limits.
  • the reactions go at lower temperature and may be conducted at higher temperature below decomposition temperature causing rupture of carbon-carbon bonds. In general, the reaction temperature will not be above 300 C. It is feasible to separate by-product water during the reaction. This may be accomplished by azeotropic distillation employing any of the Well-known azeo troping agents, but preferably excess of cyclic ketone, used as a reactant. Conversely, the reactions may be run in a closed system without azeotroping water. It appears that the driving force for the reaction is not elimination of water but reduction of the nitro-compound.
  • a mixture was prepared of 12.3 grams (0.1 mole) of nitrobenzene, 2 grams of 5% palladium on carbon and 65 ml. of cyclohexanone. The mixture was heated while distilling off water. The first water was collected when the temperature reached 161 C. Heating was continued for about 5 hours at 161-172 C. while collecting 5.6 ml. of water. Heating was then discontinued and the reaction mixture cooled, filtered and the solids washed with cyclohexanone. The filtrate and washings were combined and an aliquot analyzed by gas liquid partition chromatographic analysis. It was thereby determined that the yield of diphenylamine was of theoretical. There were traces of aniline and N-cyclohexylaniline present but no anil was detected.
  • a reactor was charged with 16.7 grams (0.1 mole) of p-nitrophenetole, 65 ml. of cyclohexanone and 2.0 grams of 5% palladium on carbon catalyst. The mixture was heated while distilling off water. Water began to separate at about 161 C. Heating was continued at 161- 173 C. for about 2 hours while collecting 6.1 grams of water. The reaction mixture was then cooled, filtered and the filter rinsed with cyclohexanone. The filtrate and washings were distilled in vacuo to a pot temperature of 110115 C. at 11 mm. Hg. The residue was cooled to about 50 C. and 50 ml. of petroleum ether added and the mixture cooled further in an ice bath and seeded. The crystalline material which separated was filtered, washed with petroleum ether and dried to obtain 11.8 grams of p-ethoxydiphenylamine, M.P. 71- 71.6" C. This represents a yield of 56%.
  • a reactor was charged with 79.5 grams (0.44 mole) of N-isopropyl-p-nitroaniline, 129 grams (1.32 moles) of cyclohexanone and 5 grams of 5% palladium catalyst supported on charcoal. The reaction mixture was heated for 2% hours at 158-168 C. during which period the theoretical quantity of water was collected. The catalyst was separated and the product subjected to gas liquid partition chromatographic analysis from which it was established that N-isopropyl-N'-phenyl-p-phenylenediamine had formed in 42.5% yield.
  • Phenol has been identified as a by-product of reactions involving cyclohexanone.
  • a plausible theoretical general reaction is that two moles of nitrocompound combine with three moles of ketone to produce two moles of product, one mole of phenol and six moles of water.
  • at least 1.5 molecular proportions of ketone should be charged for each nitro radical undergoing reaction.
  • diarylamine which consists essentially of heating at not above about 300 C. below temperature causing rupture of carbon-carbon bonds 1 molar proportion of nitrobenzene and at least 1.5 molar proportions of six-membered alicyclic hydrocarbon monoketone free from quaternary carbon in the ring with palladium catalyst and isolating diarylamine.
  • diphenylamine which consists essentially of heating at not above about 300 C. below temperature causing rupture of carbon-carbon bonds 1 molar proportion of nitrobenzene and at least 1.5 molar proportions of cyclohexanone with palladium catalyst thereby forming diphenylamine.
  • diphenylamine which consists essentially of heating at not above about 300 C. below temperature causing rupture of carbon-carbon bonds 1 molar proportion of nitrobenzene and at least 1.5 molar proportions of cyclohexanone with palladium catalyst while removing by-product water from the reaction zone thereby forming diphenylamine.
  • diarylamines which consists essentially of heating at not above about 300 C. below temperature causing rupture of carbon-carbon bonds 1 molar proportion of monoalkylnitrobenzene and at least 1.5 molar proportions of cyclohexanone with palladium catalyst and isolating alkyldiphenylamine.
  • diarylamines which consists essentially of heating at not above about 300 C. below temperature causing rupture of carbon-carbon bonds 1 molar proportion of monoalkoxynitrobenzene and at least 1.5 molar proportions of cyclohexanone with palladium catalyst and isolating alkoxydiphenylamine.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Description

United States Patent Ofiice 3,219,703 Patented Nov. 23, 1965 3,219,703 MANUFACTURE OF DIARYLAMINES FROM NITROAROMATICS Harry W. Kilbourne, St. Albans, James E. Van Verth, Huntington, and Gene R. Wilder, St. Albans, W. Va., assignors to Monsanto Company, a corporation of Delaware N Drawing. Filed Feb. 2, 1961, Ser. No. 86,606 9 Claims. (Cl. 260-571) This invention relates to the manufacture of diarylamines by aminodehydrogenation of alicyclic ketones. One embodiment of the invention relates to manufacture of diphenylramines from nitroaromatics and alicyclic ketone, which ketone serves as a source of a second aryl group. Fundamentally, the process involves heating nitroaromatic and a molar excess of cyclohexanone or other six-membered alicyclic ketone with dehydrogenation catalyst. The course of the reaction is obscure and evidently involves a complicated series of reactions. These are carried out simultaneously without isolating intermediate. The invention is not limited to any theory or opinion as to the mechanism by which the desired products form.
Aromatization requires alicyclic ketones containing six carbon atoms in the ring to which the keto group is attached but substituents may be present in this ring and condensed rings are suitable. Examples comprise cyclohexanone, 2 methylcyclohexanone, 3 methylcyclohexanone, 4 methylcyclohexanone, 3,4 dimethylcyclohexanone, 2,S-dimethylcyclohexanone, 4-ethylcyclohexanone, 4-propylcyclohexanone, 4-isopropylcyclohexanone, 4- butylcyclohexanone, 4-tert.butylcyclohexanone, 2-ethylcyclohexanone, alpha-tetralone, beta-tetralone and 2- propylcyclohexanone. In addition to saturated ketones unsaturated ketones are also useful, as for example, carvenone, menthone and 3,S-dimethyLZ-cyclohexen-l-one. Ketones containing a quaternary carbon in the ring react poorly in the present process.
The process is especially applicable to nitroaromatic hydrocarbons but is not confined thereto. The aromatic nucleus containing one or more nitro groups may contain hydrocarbon substituents but readily reducible substituents are undesirable. Hydrocarbonoxy groups or fluoro substituents may be present. Depending upon the choice of reactants a variety of diarylamines can be made by the process of this invention. Suitable nitrocompounds comprise o-ethoxynitrobenzene, p-dinitrobenzene, m-dinitrobenzene, l-nitronaphthalene, 2-, 3- and 4-nitrotoluene, 4-nitroanisole, 2,4-dinitrotoluene, 4-nitrodiphenyl, p-propoxynitrobenzene, p-ethoxynitrobenzene, p-iso propoxynitrobenzene, p-ethylnitrobenzene, p-propylnitrobenzene, p-isopropylnitrobenzene, m-ethylnitrobenzene, p-amylnitrobenzene, p-hexylnitrobenzene, p-octylnitrobenzene, p-decylnitrobenzene, p-dodecylnitrobenzene, mbutylnitrobenzene, m-tert.-butylnitrobenzene, p-tert.butylnitrobenzene, p sec-octylnitrobenzene, p tert.-dodecylnitrobenzene, p-tert.-octylnitrobenzene, p-phenoxynitrobenzene, p-cyclohexylnitrobenzene, p-fluoronitrobenzene and p-benzylnitrobenzene. Probably because of steric factors 2,6-dialkylnitrobenzenes react slowly but still give good results.
It will be appreciated that presence of radicals more reactive with the ketone than the nitro radical is disadvantageous and results in excessive side reaction. Thus, primary amino groups should be absent but secondary amino groups react more slowly under the relatively mild conditions at which aromatization takes place and may be present. For example, p-nitrodiphenylamine, N-benzyl-p-nitroaniline and N-alkyl-p-nitroanilines react to yield compounds in which alicyclic ketone is converted to aromatic amino radical in place of the nitro radical exclusively. Tertiary amine by-products formed, if any, may be separated or left in as desired. Mixtures are frequently useful as antioxidants for oxidizable substances such as natural and synthetic rubber and gasoline. Examples of N-alkylnitroanilines suitable as reactants comprise those in which the alkyl group is methyl, ethyl, propyl, isopropyl, butyl, tert.-butyl, see-butyl, isobutyl, amyl, pentyl, hexyl, octyl, tert.-octyl, see-octyl, nonyl, decyl, undecyl, dodecyl, hexadecyl and the like. In general, as the alkyl group increases in size amount of by-products is reduced.
Many dehydrogenation catalysts are known and a variety are commercially available. In general, hydrogenation catalysts also function as dehydrogenation catalysts. Examples of dehydrogenation catalysts are rhodium, ru-- thenium, platinum, palladium, Raney nickel, Raney cobalt, copper chromite, iridium, osmium, oxides of chromium and oxides of molybdenum. For the purposes of the present invention palladium is much to be preferred, is effective under milder conditions and results in higher yields. It will be appreciated, however, that other dehydrogenation catalysts are contemplated and the desired products have been prepared from reactions with other catalyst systems. Desirably, the catalyst is supported on charcoal, asbestos, alumina, pumice, kieselguhr, silica gel or barium sulfate. Amounts as low as 1% of 5% palladium on carbon give satisfactory results. The amount of catalyst, expressed as percent by weight of the final product expected from the reaction assuming theoretical yield, will depend upon the reaction rate required. Amounts within the range of 1%12% catalyst (5% palladium on carbon) efficiently catalyze the reactions although these are not the absolute limits. The reactions may be effected in the presence of elemental hydrogen providing the hydrogen concentration is not so high as to make hydrogenation predominate over dehydrogenation. The presence of hydrogen gas sometimes mitigates catalyst poisoning.
The optimum temperature for heating usually will, fall with the range of ISO-250 C. depending upon the particular ketone reacted. These are not the absolute operating limits. The reactions go at lower temperature and may be conducted at higher temperature below decomposition temperature causing rupture of carbon-carbon bonds. In general, the reaction temperature will not be above 300 C. It is feasible to separate by-product water during the reaction. This may be accomplished by azeotropic distillation employing any of the Well-known azeo troping agents, but preferably excess of cyclic ketone, used as a reactant. Conversely, the reactions may be run in a closed system without azeotroping water. It appears that the driving force for the reaction is not elimination of water but reduction of the nitro-compound.
The following examples illustrate the invention in further detail.
A mixture was prepared of 12.3 grams (0.1 mole) of nitrobenzene, 2 grams of 5% palladium on carbon and 65 ml. of cyclohexanone. The mixture was heated while distilling off water. The first water was collected when the temperature reached 161 C. Heating was continued for about 5 hours at 161-172 C. while collecting 5.6 ml. of water. Heating was then discontinued and the reaction mixture cooled, filtered and the solids washed with cyclohexanone. The filtrate and washings were combined and an aliquot analyzed by gas liquid partition chromatographic analysis. It was thereby determined that the yield of diphenylamine was of theoretical. There were traces of aniline and N-cyclohexylaniline present but no anil was detected.
A reactor was charged with 16.7 grams (0.1 mole) of p-nitrophenetole, 65 ml. of cyclohexanone and 2.0 grams of 5% palladium on carbon catalyst. The mixture was heated while distilling off water. Water began to separate at about 161 C. Heating was continued at 161- 173 C. for about 2 hours while collecting 6.1 grams of water. The reaction mixture was then cooled, filtered and the filter rinsed with cyclohexanone. The filtrate and washings were distilled in vacuo to a pot temperature of 110115 C. at 11 mm. Hg. The residue was cooled to about 50 C. and 50 ml. of petroleum ether added and the mixture cooled further in an ice bath and seeded. The crystalline material which separated was filtered, washed with petroleum ether and dried to obtain 11.8 grams of p-ethoxydiphenylamine, M.P. 71- 71.6" C. This represents a yield of 56%.
A reactor was charged with 79.5 grams (0.44 mole) of N-isopropyl-p-nitroaniline, 129 grams (1.32 moles) of cyclohexanone and 5 grams of 5% palladium catalyst supported on charcoal. The reaction mixture was heated for 2% hours at 158-168 C. during which period the theoretical quantity of water was collected. The catalyst was separated and the product subjected to gas liquid partition chromatographic analysis from which it was established that N-isopropyl-N'-phenyl-p-phenylenediamine had formed in 42.5% yield.
Phenol has been identified as a by-product of reactions involving cyclohexanone. A plausible theoretical general reaction is that two moles of nitrocompound combine with three moles of ketone to produce two moles of product, one mole of phenol and six moles of water. In this connection, it is desirable to use at least one and one-half moles of ketone per mole equivalent of nitrocompound. Thus, at least 1.5 molecular proportions of ketone should be charged for each nitro radical undergoing reaction.
It is intended to cover all changes and modifications of the examples of the invention herein chosen for purposes of disclosure which do not constitute departures from the spirit and scope of the invention.
What is claimed is:
1. The process of aromatization which consists essentially of heating at not above about 300 C. below tem perature causing rupture of carbon-carbon bonds 1 molar proportion of nitrocompound selected from the group consisting of hydrocarbon nitrocompound, and substituted derivatives thereof wherein the substituents are less reactive with the ketone than a nitro radical and are selected from the group consisting of RO, RNH and fluorine where R is a hydrocarbon radical and at least 1.5 molar proportions of six-membered alicyclic hydrocarbon monoketone free from quaternary carbon in the ring with palladium catalyst thereby converting the alicyclic ketone to aromatic amino radical in place of nitro radical.
2. The process of aromatization which consists essentially of heating at not above about 300 C. below tem perature causing rupture of carbon-carbon bonds 1 molar proportion of nitroaromatic hydrocarbon and at least 1.5 molar proportions of six-membered alicyclic hydro carbon monoketone free from quaternary carbon in the ring with palladium catalyst thereby converting alicyclic ketone to aromatic amino radical in place of nitro radical.
3. The process of making diarylamine which consists essentially of heating at not above about 300 C. below temperature causing rupture of carbon-carbon bonds 1 molar proportion of nitrobenzene and at least 1.5 molar proportions of six-membered alicyclic hydrocarbon monoketone free from quaternary carbon in the ring with palladium catalyst and isolating diarylamine.
4. The process of making diphenylamine which consists essentially of heating at not above about 300 C. below temperature causing rupture of carbon-carbon bonds 1 molar proportion of nitrobenzene and at least 1.5 molar proportions of cyclohexanone with palladium catalyst thereby forming diphenylamine.
5. The process of making diphenylamine which consists essentially of heating at not above about 300 C. below temperature causing rupture of carbon-carbon bonds 1 molar proportion of nitrobenzene and at least 1.5 molar proportions of cyclohexanone with palladium catalyst while removing by-product water from the reaction zone thereby forming diphenylamine.
6. The process of aromatization which consists essentially of heating at not above about 300 C. below temperature causing rupture of carbon-carbon bonds 1 molar proportion of p-nitrodiphenylamine and at least 1.5 molar proportions of six-membered alicyclic hydrocarbon monoketone free from quaternary carbon in the ring with palladium catalyst, thereby converting alicyclic ketone to aromatic radical in place of nitro radical.
7. The process of making diarylamines which consists essentially of heating at not above about 300 C. below temperature causing rupture of carbon-carbon bonds 1 molar proportion of monoalkylnitrobenzene and at least 1.5 molar proportions of cyclohexanone with palladium catalyst and isolating alkyldiphenylamine.
8. The process of making diarylamines which consists essentially of heating at not above about 300 C. below temperature causing rupture of carbon-carbon bonds 1 molar proportion of monoalkoxynitrobenzene and at least 1.5 molar proportions of cyclohexanone with palladium catalyst and isolating alkoxydiphenylamine.
9. The process which consists essentially of heating below 250 C. 1 molar proportion of N-alkyl-p-nitroaniline and at least 1.5 molar proportions of cyclohexanone with palladium catalyst thereby forming N-alkyl- N'-phenyl-p-phenylenediamine.
References Cited by the Examiner UNITED STATES PATENTS CHARLES B. PARKER, Primary Examiner.

Claims (1)

1. THE PROCESS OF AROMATIZATION WHICH CONSISTS ESSENTIALLY OF HEATING AT NOT ABOVE ABOUT 300*C. BELOW TEMPERATURE CAUSING RUPTURE OF CARBON-CARBON BONDS 1 MOLAR PROPORTION OF NITROCOMPOUND SELECTED FROM THE GROUP CONSISTING OF HYDROCARBON NITROCOMPOUND, AND SUBSTITUTED DERIVATIVES THEREOF WHEREIN THE SUBSTITUENTS ARE LESS REACTIVE WITH THE KETONE THAN A NITRO RADICAL AND SELECTED FROM THE GROUP CONSISTING OF RO-, RNH- AND FLUORINE WHERE R IS A HYDROCARBON RADICAL AND AT LEAST 1.5 MOLAR PROPORTIONS OF SIX-MEMBERED ALICYCLIC HYDROCARBON MONOKETONE FREE FROM QUATERNARY CARBON IN THE RING WITH PALLADIUM CATALYST THEREBY CONVERTING THE ALICYCLIC KETONE TO AROMATIC AMIKNO RADICAL IN PLACE OF NITRO RADICAL.
US86606A 1961-02-02 1961-02-02 Manufacture of diarylamines from nitroaromatics Expired - Lifetime US3219703A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US86603A US3219705A (en) 1961-02-02 1961-02-02 Manufacture of n-cyclohexyl n'-phenyl-p-phenylenediamine
US86606A US3219703A (en) 1961-02-02 1961-02-02 Manufacture of diarylamines from nitroaromatics
DEM51653A DE1280253B (en) 1961-02-02 1962-02-01 Process for the production of aromatic
GB4035/62A GB975097A (en) 1961-02-02 1962-02-02 Production of n-substituted aromatic amines

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US86603A US3219705A (en) 1961-02-02 1961-02-02 Manufacture of n-cyclohexyl n'-phenyl-p-phenylenediamine
US86606A US3219703A (en) 1961-02-02 1961-02-02 Manufacture of diarylamines from nitroaromatics

Publications (1)

Publication Number Publication Date
US3219703A true US3219703A (en) 1965-11-23

Family

ID=26774933

Family Applications (2)

Application Number Title Priority Date Filing Date
US86606A Expired - Lifetime US3219703A (en) 1961-02-02 1961-02-02 Manufacture of diarylamines from nitroaromatics
US86603A Expired - Lifetime US3219705A (en) 1961-02-02 1961-02-02 Manufacture of n-cyclohexyl n'-phenyl-p-phenylenediamine

Family Applications After (1)

Application Number Title Priority Date Filing Date
US86603A Expired - Lifetime US3219705A (en) 1961-02-02 1961-02-02 Manufacture of n-cyclohexyl n'-phenyl-p-phenylenediamine

Country Status (3)

Country Link
US (2) US3219703A (en)
DE (1) DE1280253B (en)
GB (1) GB975097A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4355180A (en) * 1980-10-16 1982-10-19 Basf Aktiengesellschaft Preparation of primary aromatic amines from cyclic alcohols and/or ketones

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3509213A (en) * 1966-10-19 1970-04-28 Uniroyal Inc Cobalt sulfide and rhenium sulfide as catalysts for reductive alkylation of aromatic amino and nitro compounds
US4431841A (en) * 1982-09-16 1984-02-14 Uniroyal, Inc. Process for making diarylamines
CA1244836A (en) * 1984-03-14 1988-11-15 Teruyuki Nagata Process for producing diphenylamines or n,n'-diphenyl- phenylenediamines
DE4100514A1 (en) * 1991-01-10 1992-07-16 Bayer Ag Di:phenylamine and derivs. prodn. from corresp. N=cyclohexylidene aniline
US5382690A (en) * 1992-08-11 1995-01-17 Mitsui Toatsu Chemicals, Incorporated Method for preparing aromatic secondary amino compound
US5536878A (en) * 1992-08-11 1996-07-16 Mitsui Toatsu Chemicals, Inc. Method for preparing aromatic secondary amino compound

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2380420A (en) * 1940-12-16 1945-07-31 William S Emerson Production of secondary and tertiary amines from nitrogen compounds
US2413598A (en) * 1943-03-23 1946-12-31 Shell Dev Catalytic conversion of alicyclic ketonic compounds

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2883362A (en) * 1953-12-30 1959-04-21 Universal Oil Prod Co Preventing the cracking of rubber by means of certain n,n,n',n'-tetra-alkyl-p-phenylene diamines
US3014967A (en) * 1957-01-11 1961-12-26 Monsanto Chemicals Preparation and hydrogenation of schiff's bases

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2380420A (en) * 1940-12-16 1945-07-31 William S Emerson Production of secondary and tertiary amines from nitrogen compounds
US2413598A (en) * 1943-03-23 1946-12-31 Shell Dev Catalytic conversion of alicyclic ketonic compounds

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4355180A (en) * 1980-10-16 1982-10-19 Basf Aktiengesellschaft Preparation of primary aromatic amines from cyclic alcohols and/or ketones

Also Published As

Publication number Publication date
GB975097A (en) 1964-11-11
DE1280253B (en) 1968-10-17
US3219705A (en) 1965-11-23

Similar Documents

Publication Publication Date Title
US3219702A (en) Manufacture of aromatic amines by aromatization
US2422013A (en) Preparation of imines
US4085141A (en) Process for the preparation of anilines meta-substituted by chlorine
US3219703A (en) Manufacture of diarylamines from nitroaromatics
US4005143A (en) Process for manufacturing aromatic diamines
US4871875A (en) Process for producing diphenylamines or N,N'-diphenylphenylenediamines
US3976697A (en) Preparation of tertiary amines
JPS5976040A (en) Diarylamine improved manufacture
US3474144A (en) Catalytic reduction of chloronitro aromatic compounds
US4026944A (en) Process for manufacturing diaminonaphthalene
US3442950A (en) Process for preparing an aminated benzene
CA1133517A (en) Preparation of n-phenyl-n'-alkylphenylenediamines
US4024196A (en) Process for the manufacture of hydroquinone
EP0630881A1 (en) Process for the preparation of diphenylamine
US2540938A (en) N-substituted diamines and preparation of the same
EP0014998A1 (en) Preparation of tertiary aromatic amines by reductive alkylation of diaryl secondary amines with ketones
US3427355A (en) Process for preparing aniline and alkyl aniline
US2063151A (en) Process of producing n-aralkyl-amino-phenols
JPS6233229B2 (en)
US3361818A (en) Process for preparing aminated benzenes from aminated cyclohexanes
US2175585A (en) Preparation of furfurylamines
US3996292A (en) Process for the preparation of aliphatic dialdehydes
US3234281A (en) Manufacture of n, n-di-sec-alkyl tertiary amines
US3150185A (en) Hydrogenation of nitrohaloaromatic compounds
US3532754A (en) Catalytic deamination of alkyl diaminobenzenes to alkyl aminobenzenes